Production of aryl indan hydrocarbons



Patented Aug. 22, 1950 rnonnorioN F ARYL lNDAN HYDROCARBONS Vladimir NJpatieff and Herman Pines, Chicago, IlLyassignorsto Universal Oil Products Company, Chicago, 111., a corporation of Delaware a, Drawing. Application June 30, 1948, Serial No. 36,274

16 Claims.

This application is a continuation-impart of our copending application Serial Number 619,430,

'=filed September 29, 1945, now 'abandoned.

This invention relates to a process for producing aryl indan hydrocarbons and particularly for producingphenyl' indan hydrocarbons and alkylated or cycloalkylated phenyl-indan hydrocarbons.

hydrocarbon which comprises reacting at ,hydrogen transfer conditions in the presence of an acid-acting catalyst a branched-chain. olefin and a meta-di-alkylated benzene hydrocarbon having as one substituent an alkyl group containing only one hydrogen atom joined to the carbon atom combined with the benzene ring.

Another embodiment of this invention relates to a process for producingan aryl indan hydrocarbon whichcomprisesl reacting in the presence of an acid-acting catalyst analkyl cyclohexene hydrocarbon and aimeta-dialkyl benzene hydrocarbon having as one substituent an alkylgroup containing only one, hydrogen atom joined to the carbon atom combined with the benzene ring. A further embodiment of this invention relates to a process for producing aryl indan hydrocarbons which comprises reacting at hydrogen transfer conditions in the presence of an acidacting catalyst, a branched-chain olefin and a benzene hydrocarbon of the formula:

7 wherein each R1, R2 and Re is selected from the group consisting of an alkyl radical, a cycloalkalkyl radical, a cycloalkylradical, and a bicycloalkyl radical.

' We have developed a method for producing indan hydrocarbons by effecting a hydrogen transfer reaction between abranched-chain ole- 'finic hydrocarbon and an aromatic hydrocarbon containing at least two and not more than five hydrocarbon group .substituents with two of said substituents in meta positions. One of said I ineta-substituentscontains atleast three carbon atoms and also a hydrogen atom combined with the carbon atom that is joined to the aromatic ring. The reaction is illustrated by the follow" ing equation wherein a: is selected from zero and 5 the small even numbers 2, 4, etc., and R1 and R2 each represents a member of the group consisting of alkyl, cyoloalkalkyl, cycloalkyl, and bicycloalkyl radicals and R3 and R4 each represent a member of the group consisting of a hydrogen atom and the radicals enumerated for R1 and R2. When R1 and R2 represent, alkyl groupsand R3 and R4 represent hydrogen atoms, the indan hydrocarbon. formed as indicated in the renowing equation is a 1,3,3,5-tetraalk'yl-i1 mtolyh indan. v a

l Cn 2n-z-HZ R2 so Similarly the production of 1,3, 3;5-tetramethyll-m-tolyl-indan from m-cymene and 2-met-hyl- Z-butene is indicated by the equation:

1,3,3,5-tetramethyl-l-m Iso-pentane tolyl-indan The formation of 1,3,3,5-tetramethyi-1-m=- B0 tolyl-indan by hydrogen transfer between iii-cymene and a methylcyclohexene' is illustrated by the following equation:

m-Oymene Methylcyclohexene-3 Methylcyclohexane CHa l,3,3,5-tetramethyl-l-mtolyl-indan Aromatic hydrocarbons which are useful as starting vmaterials in this process contain two hydrocarbon group constituents in meta positions to one another. Also one of these substituents in the m-substituted hydrocarbon must have only one hydrogen atom combined with the carbon atom that is attached to the benzene ring. Accordingly, this hydrocarbon substituent which contains the tertiary hydrogen atom also contains at least three carbon atoms. aromatic hydrocarbons have structures which may be represented by the following formula:

wherein each of R1, R2 and R3 is selected from the group consisting of an alkyl radical, a cycloalkalkyl, a cycloalkyl radical, and a bicycloalkyl radical. The combination of the dilierent R groups should be balanced so as to avoid steric hindrance. Also aromatic hydrocarbons and particularly benzene hydrocarbons containing more than three hydrocarbon substituent groups may also be used as starting material provided that such a hydrocarbon has a replaceable hydrogen atom combined with a nuclear carbon atom adjacent to the carbon atom which is combined with the group:

Such aromatic starting materials include m-cymene, 1-methyl=3-sec. butyl-benzene, 1-ethyl-3- isopropylcymene, isopropylp-Xylene, etc.

Olefinic starting materials suitable for this hydrogen transfer process have branched chains and include such hydrocarbons as trimethylethylene, dihydrolimonene, methylcyclohexene, 1,1,3-trimethyl-cyclc-hexene, menthene, etc. The exact type of olefin to be used is dependent on the catalyst and the aromatic hydrocarbon with which the hydrogen transfer is to be effected. Thus n-octene and cyclohexene, namely, olefins not possessing branched chains, when reacted with a meta-dialkyl aromatic hydrocarbon at operating conditions similar to those used with the branched-chain olefins, efiect alkylation but not hydrogen transfer.

In addition to the branched-chain monoolefins mentioned above, other olefin-acting compounds which are also utilizable in this process comprise conjugated diolefins containing a tertiary carbon These different atom, alcohols, ethers, esters of carboxylic acids, tertiary alkyl phenols including particularly tertiary butyl phenol, tertiary amyl phenol, tertiary and ditertiary alkyl benzenes such as di-tertiary amyl benzene, and the like which may be regarded as capable of forming branched-chain olefins in situ in the reaction mixture.

The process as herein described is carried out in the presence of an acid-acting catalyst at conditions necessary for the hydrogen transfer reaction. Suitable acid-acting catalysts include strong mineral acids, such as sulfuric acid, chlorosulfonic acid, fluorosulfonic acid, hydrogen fluoride, hydroxyborofiuoric acids, fiuorophosphoric acids, phosphoric acids; and Friedel-Crafts halide catalysts, particularly aluminum chic-ride, aluminum bromide, ferric chloride, zirconium chloride, and boron fluoride. Since in some cases Friedel-Crafts catalysts may cause an alkyl migration within the aromatic ring before the hydrogen transfer reaction occurs, it is sometimes advantageous to use Friedel-Crafts complexes, such as etherate, alcoholate, etc. for this reaction.

The operating conditions used in the process are dependent upon the nature of the hydrocarbons being treated and also upon the catalysts employed. When utilizing strong mineral acids,

.such as hydrogen fluoride, sulfuric acid, fiuorosulfonic acid, chlorosulfonic acid, and the like, and also Friedel-Crafts metal halides promoted by a hydrogen halide such as hydrogen chloride, theprocess is carried out at a. temperature of from about 30 to about 100 C., and at a pressure up to about 100 atmospheres. However, in the presence of hydrogen fluoride, sulfuric acid, and aluminum chloride catalysts the preferred operating temperature is generally from about 0 to about. 50 C., while in contact with ferric chloride catalyst the preferred operating temperature is from about 50 to about 100 G.

Our process is carried out in either batch or continuous type Ofoperation. In batch-type oprecovered in this distillation are utilizable in the further operation of the process. V

The process is also carried out in a continuous manner by passing the aromatic and branchedchain olefinic hydrocarbons through a suitable reactor in which they are contacted in the presence of the catalyst, the latter either as a liquid catalysts such as sulfuric .acid, ichlorosulfonic actor and the aromatic and cycloo'lefi-nic hydrocarbons are passed therethrough, the resultant hydrocarbon product generally requires no washing and drying treatment and may be distilled to separate therefrom unconverted aromatic and cycloolefinic hydrocarbons and to recover the :desired indan hydrocarbons.

In order to obtain good yields of indan hydrocarbons by our process, it is necessary to use rather carefully selected hydrocarbon fractions as charging stocks. As already indicated herein, only certain types of aromatic hydrocarbons,

namely those containing particular substituents are utilizable as starting materials to produce indan-type hydrocarbons. Thus m-isopropyltoluene, rn-secondary butyl toluene, meta-diisopropylbenzene and other aromatic hydrocarbons containing alkyl groups in meta positions to one another react readily with branched-chain ole'fins to form an indan hydrocarbon and a saturated hydrocarbon, the "latter having substantially the same carbon skeleton as that of the olefinic hydrocarbon charged to the process. .An' aromatic hydrocarbon which does not contain the aforementioned disubstitution in meta position does not react with a branched-chain olefin to give the desired hydrogen transfer reaction. Also an olefin which does not have a branched-chain such as is present in trimethylethylene, dihydrolim-onene, methylcyclopentene,

etc. acts as an alkylating agent for the aromatic hydrocarbo-n also charged to the process. Accordingly, in order to obtain hydrogen transfer rather than alkylation, it is necessary to use a dan containing a long alkyl, cycloalkalkyl or cycloalkyl group may also be converted into a detergent by neutralization with a basic compound of an alkali metal, Some of the indan hydrocarbons formed in the process are also useful as additives to improve the viscosity characteristics of lubricating oils.

The following example is given to illustrate the character of the results obtained by the use of specific embodiments of the present invention, although the data presented are not introduced. with the intention of unduly restricting the generally broad scope of the invention.

Thirty grams of m-cymene (prepared from m-bromotoluene with acetone via a Grignard. reaction, followed by hydrogenation) were reacted with 10.8 grams of methylcyclohexene in the presence of 25 grams of hydrogen fluoride. The

product obtained distilled as follows:

Out Te rgp, Pressur v Weigght,

.1 09-101 Arm. 1. 6 1. 4210 Cut .1--corresponds .to .methylcyclohexane. Cut 2=unreacted m-cymenc.

Cut 3 and 4=methylcyclohexyl-m-cymene. Cut 5 and 6 tetramethyl-l-m-tolyl-indan.

The tetranitro compound of cut 6 melted at 203 C. Anal. calcd. for CzoH2oN40at C, 54.1; H, 4.5;,

N, 12.6. Found: C, 53.7; H, 4.6; N, 12.8. The l,3,3,5-tetramethyl-l-m-tolyl-indan produced is a new compound. 1

We claim as our invention:

1. A process for producing an aryl indan hydrocarbon which comprises reacting at a hydrogen transfer temperature'of from about 30 -C.

to about 100 C. in the presence of an acid-acting ca-talysta branched-chain olefin and metadialkylated aromatic hydrocarbon having as one substituent an alkyl group containing only one hydrogen atom joined to the carbon atom combined with the aromatic ring, the last-named hydrocarbon having a hydrogen atom combined with a carbon atom of the ring which is adjacent to the carbon atom of the ring which is combined with said alkyl group.

2'. A process for producing an aryl indan hydrocarbon which comprises reacting at a hydrogen transfer temperature of from about -'30 C. to about 100 C. in the presence of an acid-acting catalyst a branched-chain olefin and a metad'ialkyl benzene hydrocarbon having as one substituent an alkyl group containing only one hydrogen atom joined to the carbon atom combined with the benzene ring, the last-named hydrocarbon having a hydrogen atom combined with a carbon atom'of the ring which is adjacent to the carbon atom of the ring which is combined with said alkyl group.

3. A process for producing an aryl indan hydrocarbon which comprises reacting at a hydrogen transfer temperature of from about 30 C. to about 100 C. in the presence of an acid-acting catalyst an alkyl-cyclohexene hydrocarbon and a meta-dialkyl benzene hydrocarbon having as one substituent an alkyl group containing only one hydrogen atom joined to the carbon atom combined with the benzene ring, the last-named hydrocarbon having a hydrogen atom combined with a carbon atom of the ring which is adjacent to the carbon atom of the ring which is combined with said alkyl group.

4. A process for producing an aryl indan hydrocarbon which comprises reacting at a hydrogen transfer temperature of from about -30 C. to about 100 C. in the presence of a strong mineral acid catalyst, a branched-chain olefin and a meta-dialkyl benzene hydrocarbon having as one substituent an alkyl group containing only one hydrogen atom joined to the carbon atom combined with the benzene ring, the last-named hydrocarbon having a hydrogen atom combined with a carbon atom of the ring which is adjacent to the carbon atom of the ring which is combined with said alkyl group.

5. A process for producing an aryl indan hydrocarbon which comprises reacting in the presence of a strong mineral acid catalyst at a temperature of from about 30 to about 100 C. a branched-chain olefin and a meta-alkyl benzene hydrocarbon having as one substituent an alkyl group containing at least three carbon atoms and having only one hydrogen atom joined to the carbonatom combined with the benzene ring,

the last-named hydrocarbon having a hydrogen atom combined with a carbon atom of the ring which is adjacent to the carbon atom of the ring which is combined with said alkyl group.

6. The process defined in claim further characterized in that said branched-chain olefin comprises a branched-chain alkene.

'7. The process defined in claim 5further characterized in that said branched-chain olefin comprises an alkyl cycloolefin. V

8. A process for producing an aryl indan hydrocarbon which comprises reacting in the presence of a strong mineral acid catalyst at a-temperature of from about 0 to about 50? C. a branched-chain olefin and a meta-dialkyl benzene hydrocarbon having as one substituent an alkyl group containing at least three carbon atoms and having only one hydrogen atom joined to the carbon atom combined with the benzene ring, the last-named hydrocarbon having a hydrogen atom combined with a carbon atom of the ring which is adjacent to the carbon atom of the ring which is combined with said alkyl group.

9. A process for producing an aryl indan hydrocarbon which comprises reacting in the presence of a sulfuric acid catalyst at a temperature of from about 0 to about 50 C. a branched-chain olefin and a meta-dialkyl benzene hydrocarbon having as one substituent an alkyl group containing at least three carbon atoms and having only one hydrogen atom joined to the carbon atom combined with the benzene ring, the lastnamed hydrocarbon having a hydrogen atom combined with a carbon atom of the ring which is adjacent to the carbon atom of the ring which is combined with said alkyl group.

10. A process forproducing an aryl indan hydrocarbon which comprises reacting in the presence of a hydrogen fluoride catalyst at a temperature of from about 0 to about 50 C. a branched-chain olefin and a meta-dia1ky1 benzene hydrocarbon having as one substituent an alkyl group containing at least three carbon atoms and having only one hydrogen atom joined to the carbon atom combined with the benzene ring, the last-named hydrocarbon having a hydrogen atom combined with a carbon atom of the ring which is adjacent to the carbon atom of the ring which is combined. with said alkyl group.

11. A process for producing 1,3,3,5-tetramethyl-l-m-tolylindan which comprises reacting a branched-chain olefin and meta-cymene in the presence of an acid-acting catalyst at a hydrogen transfer temperature of from about 30 C. to about C. r

12. A process for producing 1,3,3,5-tetramethyl-l-m-tolylindan which comprises reacting a branched-chain olefin and meta-cymene in the presence of a strong mineral acid catalyst at a temperature of from about 30 to about 100 C.

13. A process for producing 1,3,3,5-tetramethyl-l-m-tolylindan which comprises reacting a branched-chain olefin and meta-cymene in the presence of a strong mineral acid catalyst at a temperature of from about 0 to about 50 C.

14. A process for producing 1,3,3,5-tetramethyl-l-m-tolylindan which comprises reacting a branched-chain olefin and meta-cymene in the presence of a sulfuric acid catalyst at a temperature of from about 0 to about 50 C.

15. A process for producing 1,3,3,5-tetramethyl-l-m-tolylindan which comprises reacting a branched-chain olefin and meta-cymene in the presence of a hydrogen fluoride catalyst at a temperature of from about 0 to about 50 C.

16. A process for producing 1,3,3,5-tetramethyl-l-m-tolylindan which comprises reacting a methylcyclohexene and meta-cymene in the presence of a hydrogen fluoride catalyst at a temperature of from about 0 to about 50 C.

VLADIMIR N. IPATIEFF. HERMAN PINES.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,275,312 Tinker et a1. Mar. 3, 1942 2,316,108 Ruthruff Apr. 6, 1943 OTHER REFERENCES Puranen: Chem. Abs, vol. 27, 5062-3 (1933). Barbier: Chem. Abs, vol. 26, 4035 (1932). 

1. A PROCESS FOR PRODUCING AN ARYL INDAN HYDROCARBON WHICH COMPRISES REACTING AT A HYDROGEN TRANSFER TEMPERATURE OF FROM ABOUT -30*C. TO ABOUT 100*C. IN THE PRESENCE OF AN ACID-ACTING CATALYST A BRANCHED-CHAIN OLEFIN AND A METADIALKYLATED AROMATIC HYDROCARBON HAVIANG AS ONE SUBSTITUENT AN AKLYL GROUP CONTAINING ONLY ONE HYDROGEN ATOM JOINED TO THE CARBON ATOM COMBINED WITH THE AROMATIC RING, THE LAST-NAMED HYDROCARBON HAVING A HYDROGEN ATOM COMBINED WITH A CARBON ATOM OF THE RING WHICH IS ADJACENT TO THE CARBON ATOM OF THE RING WHICH IS COMBINED WITH SAID ALKYL GROUP. 